Study on preparation of nano-TiO<Subscript>2</Subscript> by W/O microemulsion reactor and its photocatalytic degradation of air pollution

Nanoscale and photocatalytically active TiO₂ is widely used in many fields, such as environmental protection, pollution control, and the self-cleaning of textile and architecture. This paper (i) describes the preparation of nano-TiO₂ in W/O microemulsion reactor, (ii) considers the photocatalytic degradation of air pollution caused by formaldehyde and toluene in terms of the bionics theory, and (iii) discusses the similarity between the photocatalytic degradation by nano-TiO₂ and the photosynthesis of a plant that makes the degradation of pollutions by nano-TiO₂ essentially important for ecologically safe treatment and recovery of natural resources. The text was submitted by the authors in English.     

Controlled radical emulsion polymerization of polystyrene

In this paper, a new water-soluble initiator system, 2-bromopropane/CuSO₄/sodium ascorbate, was used as the initiator for emulsion polymerization. Radical emulsion polymerization of styrene was successfully carried out at 80 °C by using sodium dodecylbenzenesulfonate as the emulsifier. The 2-bromopropane/CuSO₄/sodium ascorbate-initiated emulsion polymerization shows the controlled free-radical polymerization features with linear growth of molecular weight. Polystyrene with a relatively high molecular weight and a narrow molecular weight distribution can be synthesized by this method. On the other hand, stable polystyrene latex can be obtained, and the size of the polystyrene latex increased with the increase in monomer conversion.     

In-Situ Formation of BHET/Titanium Compound Nanocomposite and its Catalysis for Polyester

Summary: The tetrabutylorthotitanate (TBOT) was hydrolyzed by H₂O produced during the esterification of pure terephthalic acid (PTA) and ethylene glycol (EG), and the bis(2-hydroxyethyl) terephthalate (BHET)/titanium compound nanocomposite was in-situ formed. The effect of TBOT on the esterification and its product property has been investigated. The results show that the butyl alcohol from the hydrolysis of TBOT is almost distilled out with H₂O and there has no effect on the chemical structure of BHET caused by the introducing of TBOT. A kind of novel titanium compound is manufactured during the esterification under the existence of TBOT, which shows slice-like morphology from SEM micrographs and special XRD pattern with new diffraction peaks between 2-Θ = 6.9° and 10.2°. It is found that the BHET/titanium compound nanocomposite can act as the catalyst of polymerization of poly(ethylene terephthalate) (PET). The PET resins synthesized by in-situ formed catalyst have almost the same physicochemical properties with the commerced resins and have good spinnability.     

Microemulsion polymerization of acrylamide and styrene: Effect of the structures of reaction media

Isothermal phase diagrams of the system cetyltrimethylammonium bromide (CTAB)/n‐butanol/n‐octane/water were constructed, and the effect of the oil (n‐octane) contents on the microemulsions was studied at 40 °C. We determined the microemulsion structures of two systems, CTAB/n‐butanol/10% n‐octane/water and sodium dodecyl sulfonate (As)/n‐butanol/20% styrene/water, by conductivity measurements to investigate the polymerization of acrylamide and styrene in the two microemulsion systems. The polymerization kinetics of the water‐soluble monomer acrylamide in CTAB micelles and the different CTAB/n‐butanol/10% n‐octane/water microemulsion media [water‐in‐oil (W/O), bicontinuous (BC), and oil‐in‐water (O/W)] were studied with water‐soluble sodium bisulfite as the initiator. The maximum polymerization rate in CTAB micelles was found at the second critical micelle concentration. A mechanism of polyacrylamide formation and growth was proposed. A connection between the structures of the microemulsions and the polymerization rates was observed; the maximum polymerization rate occurred at two transition points, from W/O to BC and from BC to O/W, and the polyacrylamide molecular weights, which depended on the structures of the microemulsions, were also found. A square‐root dependence of the polymerization rates on the initiator concentrations was obtained in CTAB micelles and O/W microemulsion media. The polymerization of the oil‐soluble monomer styrene in different As/n‐butanol/20% styrene/water microemulsion media (W/O, BC, and O/W) was also investigated with different initiators: water‐soluble potassium persulfate and oil‐soluble azobisisobutyronitrile. A similar connection between the structures of the microemulsions and the conversions of styrene in CTAB/n‐butanol/10% n‐octane/water for the polymerization of acrylamide was observed again. The structures of the microemulsions had an important role in the molecular weights and sizes of polystyrene. The polystyrene particles were 10–20 nm in diameter in BC microemulsion media and 30–60 nm in diameter in O/W microemulsion media according to transmission electron microscopy. We determined the solubilization site of styrene in O/W microemulsion drops by ¹H NMR spectra to analyze the results of the microemulsion polymerization of styrene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3320–3334, 2001     

Self‐assembled polyurea macromer nanodispersion and resulting hybrid polyurea‐acrylic emulsions and films

A polyurea macromer (PUM) was synthesized and dispersed in basic conditions to form self‐assembled nanoparticles (<20 nm dispersions, up to 30 wt % aq. soln.). These nanoparticles enabled surfactant‐free emulsion polymerization to form hybrid polyurea‐acrylic particles despite the absence of a measureable water‐soluble fraction. The T_g of the starting PUM material was a strong function of the PUM's extent of neutralization and hydration (varying between 100 °C and >175 °C) due to changes in hydrogen and ionic bonding. Two separate hybrid polyurea‐acrylic emulsion systems were prepared: one by direct polymerization of (meth)acrylic monomers in the presence of the nanodispersion and a second by a physical blend of PUM nanodispersion with an acrylic latex control. The direct polymerization method resulted in a hybrid emulsion particle size that developed by a mechanism resembling conventional emulsion polymerization and was unlike that described for seeded polyurethane dispersion systems. Film hardness was shown to increase with increasing coating thickness for the hybrid film prepared by direct polymerization. The resulting mechanical properties could be explained by applying mechanical models for a composite foam structure. These results were unprecedented for normal elastomer films. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1373–1388     

Effect of the structures of microemulsions on chemical reactions

Two kinds of chemical reactions were studied in two different microemulsion systems: cetyltrimethylammonium bromide/1-butanol/10 and 25% n-octane/water and sodium dodecyl sulfonate/1-butanol/20% styrene/water. One reaction is a hydrolysis reaction, in which aspirin and 2,4-dinitrochlorobenzene were used as the hydrolysis substrates. The second reaction is the polymerization of styrene, which was initiated by using two initiators, water-soluble K₂S₂O₈ and oil-soluble 2,2′-azobis(isobutyronitrile), and, at the same time, the polymerization of acrylamide, which was initiated by NaHSO₃, was also studied. All the hydrolysis reaction experimental results show that the hydrolysis is greatly affected by the structures and the structural transitions of microemulsions. The hydrolysis rates are higher in water-in-oil (W/O) microemulsion media and decrease with the addition of water. The rates increase in bicontinuous (BC) microemulsions and decrease in oil-in-water (O/W) microemulsions. The transition points of the hydrolysis rates occurred at the two microemulsion structural transition points from W/O to BC and from BC to O/W. The polymerization relationships between the conversions of styrene, the molecular weights of polystyrene and the water contents of the microemulsion system were obtained. The effects of microemulsion structures on the sizes of the polystyrene particles and on the molecular weights of the polymers are discussed. Polystyrene particles with diameters of 10–60 nm were observed by microscopy. Our experimental polymerization results show that microemulsions are suitable as media for the production of polymers, the molecular weights and the particle sizes of which can be controlled and predicted by variations in microemulsion structures. Received: 11 July 1999/Accepted: 26 July 1999     

Preparation and in vitro Release Test of Insulin Loaded W/O Microemulsion

A W/O microemulsion of Tween‐80‐Span‐80/n‐butylalcohol/ethyl‐oleate/H₂O to envelop insulin (INS) was prepared. In order to obtain the maximum solved water, the components of microemulsion to envelop INS were chosen with the pseudo‐ternary phase diagram and the influences of temperature, salinity as well as the pH on microemulsion areas also were investigated. To test the properties of the microemulsion, the conductance was used to divide O/W, W/O and BC regions, the dynamic light scattering to evaluate the particle diameters of microemulsion, the ¹²⁵I isotope tracing method to measure the release rate of INS loaded in W/O microemulsion, and the growth inhibitory effect test to appraise the cytotoxicity on human normal cells. Results show that W/O microemulsion forms when water content below 50% in the microemulsion system. The microemulsion region decreases slightly with the increase of temperature, salinity and the decrease of pH. However, the viscosity measurements along certainly selected dilution lines to the microemulsion indicate that no phase invert occurred. Diameter of microemulsion particle increases with the addition of INS, and the increase is sharp in the first 5 days then very slightly at 68.6 nm within a month. The INS loaded W/O microemulsion possesses eminent sustaining release efficiency and the cytostatic as well as cytotoxic assays illustrate that the microemulsion can be used as drug delivery at small dosage.     

W/O、O/W型卵磷脂乳状液对CaCO3晶型的影响

Ｗ／Ｏ、Ｏ／Ｗ型卵磷脂乳状液对ＣａＣＯ３晶型的影响姚松年＊缪炜童华张操墨熊海涛（武汉大学分析测试科学系，武汉４３００７２）关键词：卵磷脂乳状液ＣａＣＯ３碳酸钙可以方解石、霰石、球霰石、胶状碳酸钙等形态存在且依次稳定性降低。珍珠是生物矿化产物，除氨基酸...     

Facile Synthesis of Polyethylenimine and Nano-TiO<Subscript>2</Subscript> Particles Functionalized PolyHIPE Beads for CO<Subscript>2</Subscript> Capture

Polyethylenimine (PEI) and titanium dioxide nanoparticles (nano-TiO₂) functionalized poly- HIPE beads were synthesized by suspension polymerization of styrene/divinylbenzene high internal phase emulsion (HIPE) containing PEI and nano-TiO₂ particles in inner phase. The products are uniform and spherical beads with average diameter of 1 mm. Characterization results showed good thermal stability and desired mechanical strength. CO₂ adsorption tests were performed with CO₂/H₂O/N₂ (1 : 1 : 8) gas mixture. Nano-TiO₂ particles distinctly improved the CO₂ adsorption performance of the polyHIPE beads, resulting in enhanced CO₂ adsorption capacity and fast adsorption/desorption kinetics. Besides, the functionalized polyHIPE beads exhibited remarkable cycle stability.     

Microemulsion polymerization of styrene stabilized by sodium dodecyl sulfate and diethylene glycol monoalkyl ether

The effects of the cosurfactants diethylene glycol monoalkyl ether [C _i H_{2 i +1}O(CH₂CH₂O) _j OH (C _i E _j ; i=4, 6 and j=1, 2)] on the formation of an oil-in-water styrene (ST) microemulsion and the subsequent free radical polymerization were studied. For comparison, the data for the C _i H_{2 i +1}OH (C _i OH; i=4, 6) systems obtained from the literature were also included in this work. Sodium dodecyl sulfate was used as the surfactant. The pseudo three-component phase diagram (macroemulsion, microemulsion and lamellar gel phases) was constructed for each cosurfactant. The primary parameters selected for the polymerization study are the concentrations of cosurfactant and styrene. The number of latex particles nucleated is much smaller than that of the microemulsion droplets initially present in the reaction system. Limited flocculation of the latex particles occurs to some extent during polymerization. Among the cosurfactants investigated, the C₄OH-containing polymerization system is the least stable. By contrast, the diethylene glycol monoalkyl ether group of C _i E _j tends to enhance the latex stability. C _i E _j is more effective in stabilizing the ST microemulsion and the subsequent polymerization in comparison with the C _i OH counterpart. Received: 24 December 1999 Accepted: 9 February 2000     

Evolution of particle morphology during the synthesis of hybrid acrylic/CeO2 nanocomposites by miniemulsion polymerization

The evolution of the morphology of an acrylic/CeO₂ hybrid latex synthesized by a two step seeded semibatch emulsion polymerization process was investigated. The seed was produced by batch miniemulsion polymerization and in the second step a neat monomer preemulsion was fed to the seed to increase the solids content and encapsulate the inorganic material. The morphology of the hybrid miniemulsion droplets, the seed and the final latex was analyzed by TEM. The morphologies achieved could be explained by theoretical equilibrium morphology maps based on the interfacial tensions of the monomeric, polymeric, inorganic and aqueous phases. © 2014 Wiley Periodicals, Inc. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 792–799     

Starved Semi-Batch Emulsion Polymerization for Polystyrene Nanolatexes Preparation With n-Pentanol as Cosurfactant

In the starved semi-batch emulsion polymerization, the n-pentanol was predissolved in the sodium dodecyl sulfate (SDS) solution as cosurfactant, for the purpose of polystyrene nanolatexes preparation. The effects of styrene (St) monomer feeding rate, n-pentanol dosage and SDS concentration on the monomer conversion (total and instantaneous conversions), the latex particles size (average volume diameter, d_v) and the latex particles number in a unit volume (N_p) were discussed. The function of n-pentanol not only debased the surface tension of the SDS solution, but also formed the smaller nanolatex particles size. With the 1.5 wt% n-pentanol dosage, 0.8 wt% SDS concentration and 6.0 mL/h St feeding rate for 6 h, the d_v and N_p of the final latex particles were 45.1 nm and 8.52×10¹⁵/ mL, respectively. The final latex solid content was 24.1%. All results were original and available compared to the state of the art.     

Effect of two Kinds of Imidazolium Ionic Liquids on the Microemulsion Polymerization of Methyl methylacrylate

Summary: In this paper, the microemulsion polymerization of methyl methylacrylate (MMA) was carried out with single and gemini ionic liquids as emulsifier including 1-N-tetradecyl-3-methylimidazolium bromide (C₁₄MIM · Br) and 1, 4-Bis (3-tetradecylimidazolium-1-yl) butane bromide (C₁₄MIM-4-C₁₄MIM · 2Br) respectively, and they were all have typical microemulsion polymerization characters of MMA, but the process of polymerization directly depends on the structure of the imidazolium ionic liquids. The structure and concentration of ionic liquids have effects on the resulted latex particle sizes of PMMA, and much smaller size latexes of PMMA could be gotten with C₁₄MIM · Br as emulsifier than C₁₄MIM-4-C₁₄MIM · 2Br in polymerization. On the other hand, the structure of emulsifier has the effects on the molecular weight (MW) and molecular weight distribution (MWD) of PMMA, so the resulting PMMA prepared from microemulsion polymerization with C₁₄MIM · Br as emulsifier has higher MW but narrower MWD than that of PMMA with the same dosage of C₁₄MIM-4-C₁₄MIM · 2Br as emulsifier.     

The Effect of Nano-SiO2 Colloid on Soap-free Emulsion Polymerization of Methyl Methacrylate and Hydroxyethyl Methacrylate

Soap-free emulsion polymerization of methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) was carried out in the presence of colloidal nano-SiO₂ particles. The effect of nano-SiO₂ level on the monomer conversion, polymerization rate (Rp), and emulsion stability was investigated. The viscosity, particle size distribution of the emulsions, surface tension, and ionic conductivity of these systems were determined. Upon the introduction of the nano-SiO₂ particles into this system, the Rp and monomer conversion increased and the average particle size of the P(MMA-HEMA) emulsion decreased in comparison to emulsions formed in the absence of nano-SiO₂. However, the particle size distribution became broader to some degree. Scanning electron microscope observations demonstrated that the shape of these latex particles were uniformly spherical. The surface tension and ionic conductivity of the system increased significantly after polymerization, but the presence of nano-SiO₂ resulted in an increase in surface tension and a decrease in ionic conductivity in comparison to the particle–free system.     

A biocompatible block glycopolymeric dispersant: synthesis,characterization, and dispersing properties for nano-TiO2

A biocompatible block glycopolymer poly(methyl methacrylate)-b-poly(3-O-allyl-α-D-glucose) (PMAG) was employed as a polymeric dispersant for the dispersion of nano-TiO₂. PMAG was prepared from methyl methacrylate (MMA) and 3-O-allyl-1,2:5,6-di-O-isopropynylene-α-D-glucose (ADG) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The obtained product was characterized by Fourier transform infrared (FT-IR) spectroscopy, proton nuclear magnetic resonance (¹H NMR) spectroscopy, and gel permeation chromatography (GPC). The copolymer showed good biocompatiblity by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. The maximum adsorption capacity for PMAG on nano-TiO₂ is 4.11 mg/g, which is in good agreement with Langmuir isotherm. Transmission electron microscopy (TEM) image indicated that nano-TiO₂ is well dispersed by PMAG. Raman and FT-IR spectra demonstrated that PMAG is absorbed onto the surface of nano-TiO₂.     

Kinetic and particle size studies of emulsion polymerization of methyl methacrylate and styrene with using polyamidoamine dendrimer as seed

The emulsion polymerization of methyl methacrylate (MMA) and styrene (St) were investigated with using polyamidoamine (PAMAM) dendrimer as seed, potassium persulfate as initiator and sodium dodecyl sulfate as emulsifier. The effects of 4.0GPAMAM dendrimer concentration, initiator concentration, emulsifier concentration, monomer concentration, and polymerization temperature on the monomer conversion and polymerization rate were investigated. At the same time, the influence of the generation of PAMAM dendrimer on latex particle size was studied also. The results showed that the monomer conversion and polymerization rate increased with increasing initiator concentration, emulsifier concentration, monomer concentration, and polymerization temperature. But polymerization rate increased firstly with an increase in the 4.0GPAMAM dendrimer from 0.03 g to 0.09 g and then decreased with further increase to 0.12 g. When the concentration of 4.0GPAMAM dendrimer less than 1.449 × 10^?4 mol/L, the kinetic equation can be expressed by Rp∝[4.0GPAMAM]^0.772[SDS]^0.562[KPS]^0.589[M]^0.697, and the activation energy (Ea) of emulsion polymerization is 62.56kJ/mol. In additional, the copolymer latex particle size decreased and possessed monodispersity with increasing the generation of PAMAM dendrimer. According to FT-IR spectrum analysis, PAMAM dendrimer is successfully incorporated into the poly(PAMAM-St–MMA) latex particles.     

Microemulsion polymerization of styrene

Initiation of polymerization in styrene oil-in-water microemulsions by water-soluble potassium persulfate of oil-soluble 2,2′-azobis-(2-methyl butyronitrile) at 70°C gave stable latexes which were bluish and less translucent than the original microemulsions. The effects of initiator concentration, polymerization temperature, and monomer concentration on the kinetics, particle size distributions, and molecular weight distributions were investigated. The kinetics of polymerization were measured by dilatometry. In all cases, the polymerization rate shows only two intervals, which increased to a maximum and then decreased. There was no apparent constant rate period and no gel effect. A longer nucleation period was found for polymerizations initiated by potassium persulfate as compared to 2,2′-azobis-(2-methyl butyronitrile). The small latex particle size (20–30 nm) and high polymer molecular weight (1–2 × 10⁶) implies that each latex particle consists of two or three polystyrene molecules. The maximum polymerization rate and number of particles varied with the 0.47 and 0.40 powers of potassium persulfate concentration, and the 0.39 and 0.38 powers of 2,2′-azobis-(2-methyl butyronitrile) concentration, respectively. This is consistent with the 0.4 power predicted by Smith–Ewart Case 2 kinetics. Microemulsion polymerizations of styrene–toluene mixtures at the same oil-water phase ratio gave lower polymerization rates and lower molecular weights, but the same latex particle size as with styrene alone. A mechanism is proposed, which comprised initiation and polymerization in the microemulsion droplets, by comparing the kinetics of microemulsion polymerization with conventional emulsion and miniemulsion polymerization systems.     

Interpenetrating polymer networks templated on bicontinuous microemulsions containing silicone oil, methacrylic acid, and hydroxyethyl methacrylate

Polydimethylsiloxane-poly(methacrylic acid—hydroxyethyl methacrylate) interpenetrating polymer networks (PDMS-P(MAA–HEMA) IPN) were formulated and polymerized simultaneously from bicontinuous microemulsion templates. Microemulsions containing reactive silicone oils and MAA/HEMA in aqueous solution were stabilized with silicone surfactants, and were then reacted at 50 °C for 3 h under an N₂ atmosphere. The formation of bicontinuous morphology was confirmed by laser scanning confocal microscopy, reversible swelling behavior, differential scanning calorimetry, texture analysis, and permeability to vitamin B₁₂ in aqueous solution. Incorporating polymerizable surfactants into the microemulsion aided in stabilizing the initial microemulsion structure during polymerization, yielding a more uniform IPN morphology with domain sizes of <200 nm at equilibrium swelling. The process developed here demonstrates a simple, single-step polymerization approach to forming IPNs from low viscosity microemulsion templates, and could potentially be extended to a variety of hydrophilic and hydrophobic monomers.     

Synthesis of monodisperse, large scale and high solid content latexes of poly(n-butyl acrylate) by a one-step batch emulsion polymerization

Seeded emulsion polymerization and agglomerating method were well-known techniques for the production of polymeric latexes with large particle size and high solid content. Obtaining latexes with monodisperse and particle size above 300 nm scale, however, was time-consuming and difficult by means of these methods. Here, stable, monodisperse latexes with the controlled particle diameter (55–650 nm) and high solid content (60 wt%) were synthesized via one-step in batch emulsion polymerization. Experimental investigations show that the particle size increased with decreasing emulsifier concentrations and increasing monomer/water ratios or electrolyte concentrations. The latex particle coagulation was considered as the dominant particle formation and growth method, which could be proved by the evolutions of particle number as well as dimension against conversion. Latex particle coagulation occurred if the particle surface covered ratio dropped between the critical surface covered ratio (θ _crit?=?0.59) and the lowermost surface covered ratio (θ _low?=?0.38). In addition,θ _crit and θ _low were increased with electrolyte concentrations.     

Preparation and photocatalytic antibacterial property of nitrogen doped TiO2 nanoparticles

Nitrogen doped TiO₂ (N-TiO₂) nanoparticles with about 30 nm in size were produced by a sol–gel method and characterized respectively by UV–vis, X-ray diffraction (XRD), Transmission electron microscopy, X-ray photoelectron spectroscopy (XPS). Their photocatalytic antibacterial properties were evaluated by the antibacterial ratio against Escherichia coli in dark and under simulated sunlight respectively. The XRD pattern showed that the doped nano-TiO₂ was mainly composed of anatase phase. The XPS spectra of the N-TiO₂ sample indicated that TiO₂ was doped by nitrogen atom. The nitrogen doping created a new N 2p state slightly above the valence band top consists of O 2p state, and this pushes up the valence band top and decreased the band gap. Which leaded to the absorption edge was red-shifted to the visible light region of UV–vis spectra of nitrogen doped nano-TiO₂ comparing with pure nano-TiO₂. The antibacterial percentage of N-TiO₂ against E. coli reached to 90 % under simulated sunlight for 2 h, which was much better than that in dark, also than that of pure nano-TiO₂. The photo-catalytic antibacterial activity was activated under visible light. The structure and integrity of cell wall and cell membrane were destructed, and even caused the bacteria death.